Phenolic condensation product and method of forming same.



UNITED STATES PATENT OFFICE Jonas w. AYLswom'n, or EAST omen. NEW-JERSEY, assrenon TO connnnsrrn' COMPANYOF AMERICA, 01 GLEN RIDGE, NEWJERSEY, A CORPORATION OF NEW mnsnr. 1 I

PHENOLIC oommnsarron PRODUCT AND METHOD or FORMING sans.

med June 2, 1911.-

To all whom it may concern:

Be it known that I, JONAS W. AYLswon'rn, a citizenv of the UnitedStates, and a resident of East Orange, in the county of Essex and StateofNew Jersey, have'invented certain new and useful Improve'- ments inPhenolic Condensation Products and Methods of Forming Same, of which Ythefollowing is a description.

This application is a division-of my application Ser. No. 496,060, filedMay 14,:

1909, entitled Composition'and process of manufacturingthe same; Theinvention'of the original application relates to and de scribescompositions for molding various articles, such as may be madefromcelluloid, hard rubber and kindred substances,nand also to theproduction of synthetic resins. The composition first mentioned may like,wise be used forthe formation of insulators,

phonograph records, and in many other con nections. Y

My invention as described in my parentapplication referred to, comprisesmore specificallyf first, the formation of a hard fusible phenol-resinfrom phenol or cresol by condensation with formaldehyde, which is thesynthetic resin above referred to, and secondly, the formation of anultimate infusible condensation product of a phenol and formaldehyde orequivalents. of these substances, this infusible product being Very hardand chemically inert. This infusible product may have whatI term a solidsolvent element or plasticity ingredient incorporated therewith, or not,according to different phases of my invention. This present applicationis concerned with the products containing such an element, and

:40,. processes for'm'aking the same.

Such products, while infusible are sufficiently plastic,

7 on application of heat as hereinafter de-' scribed, to .be shaped orpressed into form at suitable temperatures. This infusible,thermoplastic product, as I- may term it, is preferably formed from thephenol resin referred to, buta product having many of the advantages ofthis preferred product may be formed by treating various of the shellacsubstitutes now known, in a man roduct may be nor to be described. Theformed directly in the 11101. s'in the desired final shape, or it may becast into solid slabs,

- Io Drawing. Original application filed Hay 14, 1909, Serial No.498,060. I Divided and this application Serial No. 880,894.

granted March 19, 1912, The object of my invention as claimed inPatented Sept. 22, 1914.

The degree of plasticity will vary in accordand subsequently ance withvarious of the ingredients of the mass.

As 'stated,'this application will describe and-clalm a compositioncomprising a hard lnfusible phenolic-condensation product in solidsolution-or combination with a solid solvent or plasticity ingredient,either with l or without the addit1on of an ingredient of a class whichI termwater-combining elements. The solid solvent or ment-may, incertain cases, also perform the water-combining function without theaddition of a separate. water-combining element, but such a compositionis noFclaimed herein, being claimed in my Patent No. 1,020,594,

this application, is accordingly the productionof substances of thecharacter referred plasticity 'eleto, in which an ultimate infusi'blephenolic I condensation product is in solid solution or combination withsubstances of'the character referred to, the invention including thecompositions themselves and also a method for-producing the same.

As described in my parent application.

above referred to, I preferably first form the hard fusible phenol resinfrom phenol or condensation, pref-' erably with formaldehyde, asabovestated.-

cresol or equivalents, by

This resin may be produced in several ways, as will be hereinafterdescribed. In the for mation therefrom, of the ultimate condense tionproduct, or in the formation from any suitable phenol resin of a finalcondensation product embodying the advantages of my invention,formaldehyde, preferably in lymerized form, is incorporated with phenolresin, in the proportion of about 5 tol .74; per cent. of the weight ofthe resin, and dissolved therein. The solid polymerized forms'offormaldehyde are preferred because they are the only anhydrous forms in.which formaldehyde occurs. Phenol resinis non-watersoluble, andconsequently. will 1 not mix with a water solution of formaldehyde, butis a solvent when in melted or dis:

solved condition for anhydrous formaldehydel. If formaldehyde solutionis used in- 10:; 1 stead of polymerized formaldehyde, heating I esttemperature necessary to take place and continued heating at such I forseveral hours.

' and a considerable part of the formaldehyde from the solution, andconverts the remainder of the formaldehyde into the polymerized form,which then dissolves in and reacts with the resin. With this method itis more diflicult to obtain the corr ct reacting proportion of theformaldehyde component. Also, in the product claimed herein, a solventof the final product, which may also act as a thinning or anti-viscosityagent is incorporated. therewith, and, a small percentage of awater-combining element, suchas an anhydrid of an organic acid, morefully described hereinafter.

Having obtained the above mixture the same may be ast formation of thedesired articles or for the formation of rods, sheets, tubes, or slabs,or the like, from which the desired articles may subsequently be made byheat and pressure, or by forming by tools. The molds and their contentsare heated sufficiently to transform the product into a hard,infusible,chemically inert substance, the temperature to which the same is heatedin practice vary- 260 and 400 Fahrenheit, depending on the treatment ofthe phenol resin before mixing, the character of the water-combiningelement and the product solvent and the character of the molded article.The heating may be accomplished by casting in suitable steam-jacketedmolds, or by placing the molds and contents in suitable ovens for a timesufficient to allow the ing between mixture to interact and harden. Thistime may vary within wide limits, depending on the thickness of thearticle and the character of the mass. Thin sheets and small articlesmay be hardened in a few minutes, While larger masses and objects ofspecial character may require gradual heating to the lowfor the reactiontemperature, or at an elevated temperature, The ultimate product soformed will not melt at any temperature 240 to 300 F.-,

below that of its -decomposition, but will soften and becomesufficiently plastic at from to be further shaped by pressing insuitable dies or molds. gree of plasticity may be. controlled to acertain extent by the nature 'of the solvent ingredient'and proportionsthereof, and by varying the proportions of the polymerized formaldehyde,added 'to the phenol .resin.

In case the plasticity is controlled by vary-' -:ing the proportion ofthe polymerized formaldehyde, the phenol resin itself acts as. a solventfor the ultimate product to an explastic when maldehyde being lessthan-in products in i which plasticity is controlled by added sol-' ventelements.

if desired,

in suitable molds for the' The d'e-v changed phenol.

As stated, the phenol resin or fusible condensation product may beformed in several different Ways. I With the first of these methods, thephenol or cresol is heated in an autoclave to a temperature of from 260to 340 F., and maintained at such temperature. I prefer to use atemperature between 280 and 300 F., but a higher temperature isnecessary under some circumstances. The temperature to which the phenolis heated is determined by the nature of the phenol used, and the timein which it is desired to form the resin, which is correspondinglyshorter as a higher temperature is used. The melting point of theproduct formed is found by experience to vary with the use of differenttemperatures.

Formaldehyde gas, which may be formed in suitable generators, is forcedby suitable pumps into the bottom of the autoclave Where it isdistributed by-means of a finely perforated coil into a multitude ofbubbles, whichpass upward through the phenol and are absorbed thereinand combined therewith. A pressure in slight excess of'thevapor tensionof the contents of the autoclaveis maintained in the autoclave by meansof feeding compressed formaldehyde gas therein as rapidly as it combineswith the phenol. At a press'ureof 50 to 100 pounds per square inch, goodresults,may be obtained. The reaction may be carried on more rapidly athigher temperatures than those which I have above described aspreferable and convenient. The pressure used is about the same as thatof Water vaporat the temperature used.

The contents of the vessel are preferably kept in rapid circulation by apropeller or other convenient means. The reaction proceeds rapidly andprovision should'be made for carrying off the excess heat above theproper reaction-temperature, which is the temperature to which thephenol was initially heated, Such a heat in excess of that necessary tomaintain the reaction temperature will be generated by the reactionitself. The supply of formaldehyde is continued until a' samplewithdrawnfor test, shows only a very small percentage of free or un- Thesupply of gas is then stopped and a vent in the autoclave is opened forthe escape of steam, which is regulated by a suitable valve. Thecontents of the chamber are then heated to complete dehydration, whichrequires about 400 F.- of heat. -The contents are, then cooled to about240 F. and cast in ingots for subse-. quent use,"or passed into suitablemixing vessels for immediate use.

Other methods of making the phenol resin are described in my parent aplication referred to. In one of-these met ods, I may use a 35%solutionof formaldehyde in the proportion of 1000' parts of phenol to750 proportions, formaldehyde point passinproportions o formaldehydesolution given in the formulas are slightly more than the requiredamount. toallow for .losses during the process. In this method as in"Method No. 1 above described, care must betaken to avoid the presence ofany impurity which will act as an accelerator or catalytic. agent,otherwise difiiculty fusible and very viscid products will result. Forinstance, if the operation is carried out in an iron vessel, care-mustbe taken to have the iron well enameled or lined with a metalwhich willnot. modify the product. Iron and lead so modify the product as torender the latter unfit. Tin or tinned copper or nickel, are metalswhich can be used to line the vessel without modifying the product.

If crude phenol or cresol are-used, they should first be refined by.distillation to eliminate basic metallic impurities as well asmineralacids.

The phenol resinobtained by an of the methods described after completeehydra- I tion and removal of excess phenol is a hard resin, very kaurigum. V acetone,

similar in texture to copal and It is soluble in all proportions amyl,ethyl, methyl, and butyl alcohol, amylaethyl and methyl acetate,

acetic acid, acct lene tetrachlorid, and mononitro-benzene, (hi1 ofmil-bane), from which it remains unchanged after evaporation of thesolvents- It is fusible and practically unchanged when heated to 420 F.It melts' at about 220 F., but has no shar melting through variousegrees of v1scosity,'unt1l at 250 F. it may readily be thinly fluid. Itacts as a poured. and at 350 F.

weak acid toward bases with which it combines. It is soluble in shellac,resin and similar substances when fused therewith. This resin will notform the hard infusible condensation roduct described by .Smith, Story,Bae eland' andothers, (see English Patents 16,247 of 1899,

to Smith, 8875 of 1905, to Story, and U. S.

Patent 942, 699','to Bajekeland, and also U.

Patent No. 735,278to Luft, and articlev by 66 W. Kleeberg, in. theGerman publication Amialen der Uhemie (Liebig, volume 263, page 28.3,1891) when heated with basic or acid condensing agents, or alone, at anytemperature. When mixed with formaldehyde, pa'raformaldehyde ortrioxymethylene, and heated, it combines therewith and forms chemicallyinert.

such hard infusible mass when mixed with.

used in it becomes. quite' a hard infusible m, which, if not admixedwithother bodies, remains transparentand however, form 'It will not,

aldehydes in general, other than those mentioned, and i the percentageof formaldehyde or itspolymers exceed about 7% per cent.,' the excessescapes as bubbles in the mass and renders the latter useless for somepurposes.

.In' the formation of the ultimate condensation product, the

as stated, with formal ehyde which is ref erably polymerized. Thesubstances 0 this character which I consider best adapted for theurpo'se are trioxymethyle'ne and dioxyhenol resin is mixed met ylene, inan amount which is sufiicient to combine with nearly all the resin, sothat there may be no excess of formaldehyde or polymer thereof to causebubbling of the mass during the hardening operation. Such an amountmay'vary between 5 and 71} per cent. of the weight of phenol resin used.Formaldehyde, not polymerized, may be place of the'polymerizedsubstance, in which case the polymerized formaldehyde is formed byevaporation during the rocess. It is usually impracticable to make t ephe- I101 resin entirely free from uncombined phenol, and the smallvariable percentage of phenol makes it necessary in the formation ,ofthe mixture for the ultimate: product to vary the percentage ofdioxymethylene, trioxymethylene, or paraformaldehyde in the mixture withthe resin, in accordance with the percentages of freephenol, ascertainedby test. The phenol combines with a much greater proportion ofpolymerized formal-- dehyde than doesthe phenol resin. By varying thepercentage of the polymerized formaldehyde as indicated, the free phenolin the phenol resin may all be taken into' combination. The produgt thusobtained after heating proper proportions to a temperature of from 280to 400 F. or higher, is somewhat similar to the final=con- 'densationproduct described by Baekeland and others, but differs in four importantparticulars, as follows:

the phenol resin and the other elements mentioned in- First,the-ingredients of the ultimate product may be baked during thehardening operation by heating, as hereinbefore explalned, to atemperature of from 260 to 350 F. without becoming porous from gasbubbles 'otherthan such as may be. entrapped by the mass when cast, thusrendering it unnecessary to heat or eration under a closed vessels.

Secondly, the ultimate condensation prodperform the hardeningopcounteracting pressure in not so formed, when the same also includes aplasticity or solid solvent ingredient more fully described hereinaftersoftens 'suffi ciently to allow further shaping, as stated,

. it eils y above,

"hirdly, my product is tougher a'ndiless crane. in' texture than'thesubstances preknown ;th'e"ar t-, [as referred 'to because no basicaccelerating or cata- 'lhis absence of a condensing agent or otherimpurity permits the formation ofJan ultimate product which is almostcolorless, when desired.

"Fourth, the hltimate-"product .here described-and claimed maybe 'madeof exact ahddefiniteultimate-composition under perfeet"controlfwhereas,by..the known meth- 'od's in vogu e, "'an intermediateand final product are made which are not under such control, resultingin excessive losses. Economy in manufacture of the product is alsoenhanced.

The ultimate product, as claimed herein "is further ,distinguished fromthe "similar substances heretbforeknown by the incorporation therewithof a -water-combining element, and a final product solvent element invarying percentages... A

The water-combining "element takes care of traces of water which maylee-expelled during the baking operation. This results "in a' clearerand more transparent product,

although I do not regard the inclusion of this element as absolutelessential. -Examples of this class are enzoic anhydrid,

phthalic anhydrid, and any such organic anhydrids as are soluble in andmiscible with the mass, and are not decomposed at temperatures used. Thefinal product solvent element contributes greater toughness to theproduct by counteracting the brittle n nature of the ultimate productand renders the final mass plastic when heated, thus 'relieving internalstresses during the baking and hardening operations andsubsequentcooling. By final product solvents, I include only substanceswhich will dissolve the ultimate condensation product or combinetherewith at the'baking temperature, render it plastic at suchtemperature, and remain as a art of the product in the condition ofsolid solution. Examples ofsubstances of this class are naphthalene-and"some of its derivatives, s as n1 re and chloro derivatives, especiallythe mono-nitro and di-notro naphthalenes, di-mtro benzene,

preferably the meta variety, .acetanilid, ricinoleic acid, andricinelaidic acid, and

their anhydrids; benzoic acid and anhydrid, and di-phenylamin.Naphthalene which is noted among the final product solvents is asubstance which-tends to vdlatilize slowly at ordinary temperatures whenalone.- It does not, however, volatilize perceptibly at ordinarytemperatures when in .solid solution at the s'aine time it isinfusiblel'at any t'e'mp'erature'lowerthan that ofitsdecdmpp '-'l "ic'agent is'n'ece'ssa'ry or even.desirable. p k I I the solvent. or'plasticityfunction.

' glycerin.- tioned as with the ultimate condensation product, and

iizithin the proportions given insome of the following examples., .T V Irivatives mentioned when n solld SOIUlZIOII .yvith the ultimatecondensation product do not volatilize either ac e-m; temperatures orat212 F. In certain cases anhydridsof organic acids may beztddd. which"will perform both the water absorbing functionand.

Such substances are benzoicanhydrid and ricine laidic anhydrid.

n ph halene de- All of the plasticity orsolid'solvent ingredients namedare substantiallynon-volatile at room temperatures except naphthalene,which, as noted'above, volatilizesslowly when. alone;

These substances also are all very slight solubility in water and mostof them are practically non-water soluble at room temperatures. Forexample, the nitro-.

and chloro-napthalene derivatives mentioned above, the-di-nitro-benzene(meta), and ricinoleic and ricinelaidic acids are apparentlyinsoluble'inwater' at. 25 C. The practical non-water solubility of thesolvent or plasticity ingredients referred -to is a valuable feature,because-is'uch' ingredients cannot be removed froni {the mass to anyappreciable extent, by Water, even when the mass isgin comminuted form,andlfurt'hermore masses madeinclud-in gi such ingredients are not sosusceptible to .tlie influen ce of moisture in the atmosphere as arecompositions containing" ingredients such as glycerin, which are solubleto a very great extent. in water. Condensation products containing.glycerin, for example, constantly attract moisture from. the atmospherebecause of the hygroscopic nature of the The plasticity ingredients men-In this application I shall myselfto those solid solvent or'plasticityingredients which are-.practicall-y non-volatile and nondesirable by mealso all have water-soluble at room temperatures. Naphthalene will notbe claimed herein, being claimed in my application Serial No. 694,644,

3 filed May 2, 1912, and ,phthalic acid or anhydrid also will not beincluded in the claims of this application, as the solid solventelement, being above.

For special uses, I may also advantageously add small percentages ofacid catalytic or condensing agents when mixing the phenol resin and theotheringredients for the purpose of causing the final reaction to 1specificallymentioned in claims in my Patent No. 1,020,594, referredto-l' lamin hydrochlorid, and pinene-hy ensue more rapidly and at alower temperav 'ening reaction can be made totake place at temperaturesmuch below 250 F without such agents the reaction proceeds much moreslowly and at higher temperatures. Such a composition is particularlywell suited for hard varnish and lacquers by mixing and dissolving inalcohol, or equivalent volatile solvents, and when dried heatingmoderately in a steam oven. Suitable chemically inert pigments andfillers may be incorporated with the-mass when desired% The mass of theultimate condensation product is normally of amber color andtransparent. It may be, madepr'actically colorless if specialprecautions are taken to exclude color-giving impurities from the phenoland to exclude oxygen during subsequent heat treatment. It may. also, ifde- -s1red, be given any desired color by the addition of suitablepigments. Chemically inert cheaper substances in powdered -or fibrousform may be incorporated with the mass before bakin in widely varyingper cents, when desiretf Preferred formulae for masses which are to behardened in molds without subsequent pressing operations areas followsFor light colored and transparent products.

Parts in! weight. (1.) Phenol resin 100 Polymerlzed formaldehyd 5 to 7Benzoic anhydrld 5V to 10 (2.) Phenol resin 100 Naphthalene 5 to 10-lnlymerized formaldehyde 5 to 7 (3.) Phenal resin 1 Benzoic anhydrid 2to 4 Naphthalene 5 to 10 Try-oxymethyleneu u 5 to 8 For wine coloredproducta. r PM by weight. (4.) Phenol resin 100 Meta dl-nitro benzene 5to 10 Paraformaldehyde; 5 to 7 For non-melting plastic compositions.

- Parts by weight. (5.) Phenol resin 100 aphthalene 10 to 40,araformaldeh de- 5 to 10 .(B.) Phenol resin 100 Naphthalene... 101:0 20Benzoic anh drid 1- to 5 Paratormal ehyde 5'to 10 (7.) Phenol resin 100Meta di-nltro benzene 10 to 50' Parai'ormaldehyde 5 to 7 (8.) Phen resin100 Di-nltro benzene- 10-to 40 Benzoic anhydrid 1 to 5- Par ormaldehyde5 to 8 (9.) Phen l resin 100 Acetanilid 7 to 30 Paratormaldehyde to 8(10.) Phenol resin Tetra chloro naphthalene 10 to 25 Benzoic anhiydridto Paratormal ehyde 5 to 8 (11.) Phenol resin Mono-nitro naphthalene- 7to 30 Paraformaldehyde 6 to 8 Benzoic anhydrid l 1 to 5 The specificgravities and other qualities of variousof these compositions which'aregiven merely as follows:-

Parts by) weight. Phenol resin 102} spggi i'ic Fgravity 1.257 at asexamples, were found to be 1 Benzolc anhydrid--- 1 Color, lightlaratormaldehyde 9 sniper, tranmarenpus Phenol resin 100 c Y-Paraformaldehyde 6i ggggb ht amber Phenol resin 100 l'helapylacetanid(acetani- 13} a'; %g F g i figi I I 9 {zg g i 10s ange tin transparent.

cno resn Specific gravity 1.324. Tetrn-chloro na hthalene 20 gfi i zJpaiescentamber vcolor.

eno

Benzolc anhydrm Deep red wine co1or,

resin '100 Di-nitro benzene (meta) 40F gravity 1317' Paratormaidehyde 6tmrnsparenl and e The specific gravity of the phenol resin used wasfound to be 1.240. This substance is transparent and varies in tint fromcolorless to a dark coifee shade.

In all of the formulae given above for the ultimate condensationproduct, the ingredients are mixed and freed from air bubbles bystanding in molten condition or by vacuum treatment or by centrifugaltreatment at temperatures below 250 'F. or freed from air bubbles in anyother suitable manner. The mass is then poured into molds and ispreferably heated to a'temperature of from 260 F. to 270 F. at whichtemperature it is maintained for a, suflicient time to-render the massinfusible, and subsequently is heated for a short time to a temperatureof 300 to 350 F. r The ingredients may also heated to from 320,to 350 F.under counteracting pressure, as is done in the art of'vulcanizing'rubber. When no counteracting pressure is used, fromone-half to four hours is required before the final temperature may bereached, this time varying with the thick- .ness of the object molded.The plastic compositionsindicated inthe formulae 5 to 11 .becomesufiiciently plastic to mold at from 240 to'300 F.

By my invention a composition is formed which is infusible and hard, butis thermoplastic, is chemically inert, and is insoluble in wa thefollowing solvelrfihlco' o ethyl, methyl, amyl or butylic) ether,chloroform, carbon bi-sul d, carbon tetrachlorid, acetylene tetrachloid, acetone, benzone, camphor oil, turpentine, melted waxes, petroleum,and mineral and vegetable oils.

The shellac substitutes previously referred' to. are substances wellknown as a class, being synthetic resins, more or less fusible andsoluble, which are intended to be used'as substitutesfor natural resin,colophony, etc. They are usually formed by the 5 condensation of aphenol and formaldehyde,

which are incorporated together in different proportions in differentproducts. The phenol resin made and described by me belongs to thisclass, but has the special characteristics described which render it es:

- pecially useful in the preparation of my ultimate, infusible product.

The phenol resin described is, as I have stated, completely anhydrouswhen heated to about 400 F. for complete dehydration. \Vhen so heatedall'the water, both free and combined, is driven off from the product.The ultimate fusible product formed by the reaction between such ananhydrous phenol resin-and an added amount of anhydrous formaldehyde orits polymers, asdescribed and claimed herein, is also anhydrous, asstated, if the small amount of water evolved by the reaction between theresin and the added -formaldehyde is removed or is per manently fixed bycombination with a water-combining element, such as I have described.That is, in the ultimateinfusible product, there may be no water, eitherfree or combined, as in the case of the phenol resin,

if the water evolved by the reaction between the added formaldehyde andthe resin is all removed by proper heating which may be done when theproduct is in thin sheets or small pieces If however, this water is notall removed by heating, and a water-combining ingredient is present inthe mass, as stated, the water evolved is combined with thewater-combining .element, and is permanently fixed' to form a harmlessingredient in the mass. Thus, for

example, if phthalic or benzoic enhydrid is used as the water-combiningelement, as stated, the water combines with the same to form thecorresponding acid, as stated.

The products described and claimed, it should be noted, do not containhydrochloric acid or other hydro-halogen acid, as is the case when anorganic acid chlorid, such as benzoyl chlorid, is used as anaccelerating agent in a process for forming a phenolic condensationproduct, as-has been proposed.

' In this latter case any conversion of the chlorid into benzoic acid byreaction with water in the mass, which may occur, is'aocompanied by theformation of hydrochloric acid, which is harmful for many.

purposes, especially when the product is to be used as an insulator.

The term fusible ap caring in the claims as qualifying a pro uct such asmy phenol resin, denotes a product which melts and becomes liquid, whensufficiently heated,

under atmospheric pressure; The term infusible in the claims of thisapplication, as qualifying my'ultimate product, denotes a substancewhich does not flow or become liquid, when heated to any temperature,under atmospheric pressure. en an ultimate product solvent element isadded, or an excess of phenol resin is used as a solvent for theultimate product, as stated, the mass becomes sufficientl plastic to" bereadily pressed or molde to shape, but does not of phenol for The wordphenol as employed-in the claims is intended to include the equivalentsthe purpose of this invention, and the word include the polymers andother recognized equivalents of formaldehyde.

formaldehyde is intended to Having now described my invention what 1 Iclaim as new and desire to protect by Letters Patent is: l

"1. As a new composition of matter, a solid solution of a. phenolicultimate infusible condensation product and a substance which ispractically non-water soluble and non-v volatile at room temperatures.and which dissolves in such product at an elevated temperature andrenders the mass plastic at such temperature, said composition beingfree from any hydro-halogen acid, substantially as described.

2. As a new composition of matter, a solid body comprising a resinizedphenol ultimate reaction product containing a substance 7which.dissolves in such product at an elevated temperature and rendersthe body plastic at such temperature, the said body. eing free from anyhydro-hologen acid,

and infusible and insoluble in alcohol or water, and the said substancebeing one which is practically non-volatile at room temperatures, whosemelting point is substantially lower than its boiling point and being ofsuch a'character and proportion,

and so united within said product, as to substantially incapable ofremoval from masses of appreciable thickness or size thereof, or bywashing the body in comminuted form with water, substantially asdescribed.

3. As a new composition of matter, a solid solution of a phenolformaldehyde ultimate infusible, insoluble condensation product and bothwater-combining and final product product consisting in incorporatingwith afusible phenol resin formaldehyde of a quan-- tity just sufficient.to combine with substantially all of the same,

together with a final product solvent element which will dissolvetherein on application of heat, and heating" the mass sufficiently tocausethe reaction to I ensue and the mass to taining the product solventelement in solid solution, substantially as described.

7. The process of forming a hard infusible product consisting inincorporating with a fusible phenol resin formaldehyde of a quantityjust suflicient to combine with nearly all of the same, together with awater combining element and a final product solvent element, and heatingthe mass sufiiciently to cause the reaction to ensue and the mass to betransformed into a hard infusible chemically inert product,substantially as dc scribed.

8. The product consisting in incorporating with a fusible phenol resin:1 polymerized formaldehyde just sufiicient in amount to reactwithsubstantially all of the same, together with a final product solventelement, and heating the mass sufiiciently to cause the reaction tobetransformed into a hard infusible chemically'inert product,substantially as described.

9. The process of forming a hard infusible product consistinginincorporating with a fusible phenol resin a polymerizedformalde-,hydejust sutficient in amount to combine scri hard infusible withsubstantially all of the same, together with a water combining elementand a'final product solvent element, and heating themass sufiiclently tocause the-reaction to en-- sue and the mass to be transformed into achemically inert product, substantially as described.

10. The process of forming a hard infusible product consisting inincorporating with a fusible 1phenol resin from 5 to 7% per cent. of apo ymerized formaldehyde together witha substance which will unite withwater expelled during subsequent heating and a substance which will actas a solvent for the final product, and heating the mass sulfi cientlyto cause the reaction to ensue and the mass to be transformed into ahard infusible cherlrggally inert product, substantially asde- 11. Theprocess of forming a hard infusible product consisting in incorporatingwith a fusible phenol resin from 5 to 7% percent. formaldehyde togetherprocess of forming a hard infusible isfy the phenol, and which is suwith a substance whichwill dissolve in the final condensation product atthe baking temperature, and render the same plastic at such temperatureand remain in solid solution in the same, and baking the same at a'suflicient temperature for a sufiicient time to transform the mass intoa hard infusible chemically inert product, substantially as described.12. The process of forming a hard infusibleproduct consisting inincorporating with a fusible phenolresin from 5 to 7% per cent. of apolymerized formaldehyde together with an organic anhydrid soluble ormiscible wit the mass and .a finalproduct solvent element, and heatingthe mass at a suflicient temperature for a suflicient time to transformthe mass into a hard infusible chemically inert product, substantiallyas descri ed.

13. The process of forming a hard infusi- -ble product consisting indehydrating a hard fusible phenol. resin, incorporating therewith from 5to 7% per cent. of formaldehyde free from water and a final productsolvent element, and heating the mass at a suflicient temperature for asufiicient tune to transform the mass into a hard infusible chemicallyinert product, substantially as described. p

14. The process of formlng a hard 1nfu s1-' ble product consisting inincorporatlngwith a fusible phenol-formaldehyde condensation product inwhichv the folmaldehyde is not quite sufiicientin quantity to com letelysatstantlally free from water, an amount'of formaldeh do just sufiicientto combine with the ee phenol and with the fusible condensation product,without any excess of formalde-.

de, and an ultimate product solvent element, and heatingthe mass atatemperature and for a time suflicient to transform the product into ahard infusible chemically inert substance, substantially as described.

This specification, signed and witnessed this 22d. day of May 1911.

JONAS W. AYLswoRTH.

Witnesses:

Dm SMITH, ANNA R. KEEHM.

